CN101891619A - Contain carboxyl (methyl) acrylate and manufacture method thereof - Google Patents
Contain carboxyl (methyl) acrylate and manufacture method thereof Download PDFInfo
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- CN101891619A CN101891619A CN2010101828497A CN201010182849A CN101891619A CN 101891619 A CN101891619 A CN 101891619A CN 2010101828497 A CN2010101828497 A CN 2010101828497A CN 201010182849 A CN201010182849 A CN 201010182849A CN 101891619 A CN101891619 A CN 101891619A
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Abstract
The invention provides a kind of in fields such as coating and coated material, civil construction material, electronic material, photoelectron material, medical material suitable novel carboxyl (methyl) acrylate that contains, this contains carboxyl (methyl) acrylate by formula (I) or (I ') expression, wherein, among formula (I) and (I '), R represents hydrogen atom or methyl, and A represents alkylidene group.
Description
Technical field
The present invention relates to novel carboxyl (methyl) acrylate and the manufacture method thereof of containing.
Background technology
In the past, contain carboxyl (methyl) acrylate as 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydrophthalic acid etc., not only in fields such as coating, coated material and civil construction material, also at the electronic material that is used for semi-conductor, liquid crystal, with optical fiber, optical lens etc. is the photoelectron material of representative, and even uses in the extensive fields such as medical material.Like this contain carboxyl (methyl) acrylate, the constituent as the radiation-curing resin combination directly uses with monomeric form sometimes, (methyl) acrylic ester copolymer with other uses as multipolymer sometimes.And, with regard to aforementioned multipolymer, make the carboxyl that contains in the multipolymer further with after the reactions such as epoxy group(ing) re-use (for example, with reference to patent documentation 1 or patent documentation 2) sometimes.
Patent documentation 1: TOHKEMY 2002-220552 communique
Patent documentation 2: TOHKEMY 2008-216563 communique
On the other hand, be accompanied by the development of technology in recent years, people's demand is more high performance compound aspect each characteristic such as the transparency, hardness, chemical proofing, water tolerance.Require with reference to these, for example, the transparency of aforementioned 2-(methyl) acryloxy ethyl phthalic acid can not be said so fully, in addition, the hardness of 2-(methyl) acryloxy ethyl hexahydrophthalic acid and water tolerance can not be said so fully or the like, exist more hope and improve part.
Summary of the invention
Problem of the present invention provide a kind of in fields such as coating and coated material, civil construction material, electronic material, photoelectron material, medical material suitable novel carboxyl (methyl) acrylate and the manufacture method thereof of containing.
One embodiment of the present invention relates to by what following formula I was represented and contains carboxyl (methyl) acrylate.
(in the formula I, R represents hydrogen atom or methyl, and A represents alkylidene group.)
In addition, one embodiment of the present invention relates to the manufacture method of being represented by formula I that contains carboxyl (methyl) acrylate, it is characterized in that, make the 5-norbornylene of being represented by following formula II-2,3-dicarboxylic anhydride and hydroxyalkyl (methyl) acrylate of being represented by following formula III react.
(in the formula III, R represents hydrogen atom or methyl, and A represents alkylidene group.)
Further, one embodiment of the present invention relates to and contains carboxyl (methyl) acrylate by following formula (I ') expression.
(formula (I ') in, R represents hydrogen atom or methyl, A represents alkylidene group.)
Further, one embodiment of the present invention relates to the manufacture method that contains carboxyl (methyl) acrylate by formula (I ') expression, it is characterized in that, make the norbornane-2 of following formula (II ') expression, 3-dicarboxylic anhydride and react by hydroxyalkyl (methyl) acrylate that formula III is down represented.
(in the formula III, R represents hydrogen atom or methyl, and A represents alkylidene group.)
According to the present invention, can provide a kind of in fields such as coating, coated material, civil construction material, electronic material, photoelectron material, medical material suitable novel carboxyl (methyl) acrylate and the manufacture method thereof of containing.
Embodiment
The embodiment that contains carboxyl (methyl) acrylate and manufacture method thereof of the present invention is described in detail.Here, said (methyl) vinylformic acid is represented vinylformic acid or methacrylic acid.
Of the present invention to contain carboxyl (methyl) acrylate be novel cpd, by formula I down or (I ') expression.
In aforementioned formula I and (I '), R is hydrogen atom or methyl.A can example illustrates methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylene, pentylidene, hexylidene, inferior heptyl, alkylidene group such as octylene, wherein, be preferably the alkylidene group of carbonatoms 1～6, the more preferably alkylidene group of carbonatoms 1～3, more preferably ethylidene.
As the object lesson of representing by formula I that contains carboxyl (methyl) acrylate, can enumerate by the 5-norbornylene-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid of following formula (I-1) expression, by the 5-norbornylene-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid of following formula (I-2) expression.
As the object lesson that contains carboxyl (methyl) acrylate, can enumerate by the norbornane-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid of following formula (I '-1) expression, by the norbornane-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid of following formula (I '-2) expression by formula (I ') expression.
The manufacture method that contains carboxyl (methyl) acrylate by aforementioned formula I or (I ') expression is characterised in that, the 5-norbornylene-2 that formula II is represented, the norbornane-2 of 3-dicarboxylic anhydride or following formula (II ') expression, hydroxyalkyl (methyl) acrylate that 3-dicarboxylic anhydride and following formula III are represented reacts.
By the norbornane-2 of aforementioned formula (II ') expression, the 3-dicarboxylic anhydride is known compound, for example, can be by the 5-norbornylene-2 that formula II is represented, the 3-dicarboxylic anhydride carries out hydrogenation and obtains.Hydrogenation reaction in the presence of hydrogenation such as palladium-carbon usefulness catalyzer, is carried out under atmosphere of hydrogen usually.
In the aforementioned formula III, R is hydrogen atom or methyl.A can example illustrates methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylene, pentylidene, hexylidene, inferior heptyl, alkylidene group such as octylene, wherein, be preferably the alkylidene group of carbonatoms 1～6, the more preferably alkylidene group of carbonatoms 1～3, more preferably ethylidene.As the object lesson of the hydroxyalkyl of representing by formula III (methyl) acrylate, can enumerate (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, the own ester of (methyl) vinylformic acid hydroxyl etc.
Contain carboxyl (methyl) acrylate for what obtain aforementioned formula I or formula (I ') expression effectively, with respect to the 5-norbornylene of representing by formula II-2,3-dicarboxylic anhydride or by the norbornane-2 of formula (II ') expression, 1 mole of 3-dicarboxylic anhydride, preferred hydroxyalkyl (methyl) acrylate of being represented by logical formula III that uses 0.6～1.5 mole more preferably uses 0.9～1.2 mole.If aforementioned usage quantity is that then speed of response is fast more than 0.6 mole, not residual acid anhydrides.On the other hand, if be below 1.5 moles, then therefore resultant and do not reacted by (methyl) acrylate that formula III is represented is difficult to generate by product.
In addition, can use arbitrarily in the reaction as benzene,toluene,xylene, ethyl acetate etc. reaction is the inert solvent.
In reaction system of the present invention,, therefore, preferably add stopper because reaction raw materials and resultant of reaction have unsaturated double-bond.As stopper, can use quinhydrones, hydroquinone monomethyl ether, tert-butyl catechol, tertiary butylated hydroquinone, 2,4 dimethyl 6 tert butyl phenol, 2,6-Butylated Hydroxytoluene, para benzoquinone, 2,5-phenylbenzene para benzoquinone, thiodiphenylamine, pentanoic etc.Wherein, as when containing carboxyl (methyl) acrylate and store and when use painted few stopper, be preferably hydroquinone monomethyl ether.
The addition of stopper is preferably 5～2000ppm (weight), more preferably 10～500ppm with respect to carboxyl (methyl) acrylate that contains that obtains.If the addition of aforementioned stopper is more than the 5ppm, then the additive effect of stopper is abundant, can not produce gelation.In addition, if be below the 2000ppm, then contain carboxyl (methyl) acrylate and can not hinder polyreaction.
In addition, in reaction, in order to prevent the polymerization of reaction solution, preferably to being blown into molecularity oxygen in the reaction system.As molecularity oxygen, preferably use with the state that has diluted, be fit to use air, be more suitable for using dry air.The usage quantity of molecularity oxygen according to the shape of reactor, stir power etc. and suitably select, preferably with respect to containing 1 mole of carboxyl (methyl) acrylate, be blown into the speed of 5～500mL/ minute (is 25～2500mL/ minute as air).The usage quantity of aforementioned molecularity oxygen is more than 5mL/ minute the time, prevents polymeric effect height.For below 500mL/ minute the time,, therefore do not contain the loss of carboxyl (methyl) acrylate owing to reaction raw materials is not expressed into outside the reaction system.
Temperature of reaction is so long as 5-norbornylene-2,3-dicarboxylic anhydride or norbornane-2, the temperature that 3-dicarboxylic anhydride and hydroxyalkyl (methyl) acrylate reacts gets final product, and there is no particular restriction, usually be preferably 60 ℃～120 ℃, more preferably 90 ℃～110 ℃.If temperature of reaction is more than 60 ℃, speed of response height then, if be below 120 ℃, then can not gelation.
In addition, reaction can be carried out under normal pressure, also can under reduced pressure carry out.
Carboxyl (methyl) acrylate that contains of the present invention by above method manufacturing has unsaturated link(age), therefore polymerization separately, perhaps with aliphatics (methyl) acrylate, aromatic series (methyl) acrylate etc. other can the polymeric polymerization of unsaturated monomers.Method as making polymkeric substance can adopt known method such as radical polymerization, ionic polymerization to carry out polymerization.For example, in the presence of polymerization starter, make by methods such as mass polymerization, solution polymerization process, suspension polymerization, emulsion polymerizations.The polymkeric substance that obtains can with contain resin combination such as unsaturated group resin, unsaturated polyester, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate, use as various resin combinations.In addition, reaction backs such as the carboxyl that is present in the polymkeric substance and epoxy compounds are used.
In addition, carboxyl (methyl) acrylate that contains of the present invention is cured by radioactive rays or heat, therefore, is useful as the solidified nature composition.Radiation-curing is undertaken by ionization or such micropartical irradiation or the such chemical rays of ultra violet radiation of electron rays.When being cured, under the state that comprises various photosensitizerss or Photoepolymerizationinitiater initiater, carry out by chemical rays.In addition, thermofixation is undertaken by usual method.
By utilizing above character, carboxyl (methyl) acrylate that contains of the present invention is useful in purposes such as coating and coated material, civil construction material, electronic material, photoelectron material, medical material.
Embodiment
Next, enumerate embodiment and be specifically described, but the present invention is not limited to these embodiment.
What embodiment 1 and 2 related to formula I contains carboxyl (methyl) acrylate, and what embodiment 3 and 4 related to formula (I ') contains carboxyl (methyl) acrylate.
＜embodiment 1 〉
In 500 ml flasks of stirrer, thermometer, air leading-in conduit and prolong are installed, add 5-norbornylene-2, (Hitachi Chemical Co., Ltd. makes the 3-dicarboxylic anhydride, trade(brand)name: carbic anhydride (Himic anhydride)) (Nippon Shokubai Kagaku Kogyo Co., Ltd makes, trade(brand)name: HEMA) 200g, hydroquinone monomethyl ether 0.067g for 250g, 2-hydroxyethyl methacrylate.Then, while the speed that stirs with 100mL/ minute is blown into dry air, is warming up to 105 ℃ and makes it begin reaction.Reaction is controlled at 100～105 ℃, makes its reaction after 4 hours, and acid number has reached 198mg KOH/g, and therefore reaction finishes, and obtains 5-norbornylene-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid 440g (64.5 ℃ of fusing points).
Mensuration 5-norbornylene-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid
1H-NMR wave spectrum and IR wave spectrum obtain following wave spectrum.Thus, be confirmed to be 5-norbornylene-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid.
Just
1The H-NMR wave spectrum is dissolved in deuterochloroform with sample and makes solution, puts into the test tube of φ 5mm, and the 400MHz nuclear magnetic resonance device " AV400M " that adopts BRUKER company to make is measured.In addition, with regard to the IR wave spectrum, adopt fourier-transform infrared spectrophotometer (JIR-6500 that NEC is made) to measure.These measuring methods are also identical in following embodiment.
1H-NMR(400MHz，CDCl
3)：δ1.33-1.81(2H，m)，δ1.97(3H，m)，δ3.17-3.89(4H，m)，δ4.19-4.40(4H，m)，δ5.60(1H，m)，δ6.14(1H，m)，δ6.21-6.32(2H，m)
IR(KBr)：2974，1774，1736，1705，1174，1087，908，723cm
-1
＜embodiment 2 〉
In 500 ml flasks of stirrer, thermometer, air leading-in conduit and prolong are installed, add 5-norbornylene-2, (Hitachi Chemical Co., Ltd. makes the 3-dicarboxylic anhydride, trade(brand)name: carbic anhydride) (Nippon Shokubai Kagaku Kogyo Co., Ltd makes, trade(brand)name: HEA) 200g, hydroquinone monomethyl ether 0.064g for 250g, vinylformic acid 2-hydroxy methacrylate.Then, while the speed that stirs with 100mL/ minute is blown into dry air, is warming up to 105 ℃ and makes it begin reaction.Reaction is controlled at 100～105 ℃, makes its reaction after 4 hours, finishes reaction, obtains 5-norbornylene-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid 408g (62.0 ℃ of fusing points).
Mensuration 5-norbornylene-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid
1H-NMR wave spectrum and IR wave spectrum obtain following wave spectrum.Thus, be confirmed to be 5-norbornylene-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid.
1H-NMR(400MHz，CDCl
3)：δ1.33-1.80(2H，m)，δ3.17-3.59(4H，m)，δ3.87-4.34(4H，m)，δ5.88(1H，m)，δ6.11-6.32(2H，m)，δ6.45(1H，m)
IR(KBr)：2985，1774，1743，1716，1272，1187cm
-1
＜embodiment 3 〉
At first, as described below, synthetic norbornane-2,3-dicarboxylic anhydride.
In the 1L autoclave of stirrer, thermometer is installed, add 5-norbornylene-2, (Hitachi Chemical Co., Ltd. makes the 3-dicarboxylic anhydride, and trade(brand)name: carbic anhydride) 400g, tetrahydrofuran (THF) 400g, palladium carbon catalyst (metallic palladium charge capacity 5%) 0.4g are warming up to 60 ℃.Import compression hydrogen, making the pressure in the autoclave is 3.0MPa, begins reaction.Sustainable supply hydrogen makes the pressure in the autoclave maintain 3.0MPa often, finishes reaction in the moment that does not consume hydrogen.Filtering reacting liquid is removed palladium carbon catalyst, concentrates with Rotary Evaporators and removes tetrahydrofuran (THF).After concentrating, adopt acetone, carry out recrystallization, obtain norbornane-2 thus, 3-dicarboxylic anhydride 355g.
Next, in 500 ml flasks of stirrer, thermometer, air leading-in conduit and prolong are installed, add the norbornane-2 that obtains, (Nippon Shokubai Kagaku Kogyo Co., Ltd makes, trade(brand)name: HEMA) 200g, hydroquinone monomethyl ether 0.067g for 3-dicarboxylic anhydride 250g, 2-hydroxyethyl methacrylate.Then, while the speed that stirs with 100mL/ minute is blown into dry air, is warming up to 105 ℃ and makes it begin reaction.Reaction is controlled at 100～105 ℃, makes its reaction after 6 hours, and acid number is 190mg KOH/g, therefore, finishes reaction, obtains the norbornane-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid 432g of light yellow transparent liquid.
Mensuration norbornane-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid
1H-NMR wave spectrum and IR wave spectrum obtain following wave spectrum.Thus, be confirmed to be norbornane-2-methacryloxyethyl oxygen base carbonyl-3-carboxylic acid.
1H-NMR(400MHz，CDCl
3)：δ1.47(4H，m)，δ1.79(2H，m)，δ1.97(3H，dt)，δ2.58(2H，m)，δ3.02(2H，m)，δ4.24-4.36(4H，m)，δ5.59(1H，m)，δ6.15(1H，m)
IR(KBr)：2964，1741，1720，1166cm
-1
＜embodiment 4 〉
In 500 ml flasks of stirrer, thermometer, air leading-in conduit and prolong are installed, be added in the norbornane-2 that obtains among the embodiment 3, (Nippon Shokubai Kagaku Kogyo Co., Ltd makes, trade(brand)name: HEA) 177g, hydroquinone monomethyl ether 0.064g for 3-dicarboxylic anhydride 250g, vinylformic acid 2-hydroxy methacrylate.Then, while the speed that stirs with 100mL/ minute is blown into dry air, is warming up to 105 ℃ and makes it begin reaction.Reaction is controlled at 100～105 ℃, makes its reaction after 5 hours, and reaction finishes, and obtains the norbornane-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid 414g of light yellow transparent liquid.
Mensuration norbornane-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid
1H-NMR wave spectrum and IR wave spectrum obtain following wave spectrum.Thus, be confirmed to be norbornane-2-acryloxy ethyl oxygen base carbonyl-3-carboxylic acid.
1H-NMR(400MHz，CDCl
3)：δ1.47(4H，m)，δ1.68-1.80(2H，m)，δ2.59(2H，m)，δ3.02(2H，m)，δ4.25-4.41(4H，m)，δ5.87(1H，m)，δ6.10-6.21(1H，m)，δ6.40-6.48(1H，m)
IR(KBr)：2966，1780，1728，1186cm
-1
Claims (4)
1. one kind contains carboxyl (methyl) acrylate by what following formula I was represented,
In the formula (I), R represents hydrogen atom or methyl, and A represents alkylidene group.
2. further have on the two keys in the norbornylene of the described described formula I of claim 1 hydrogen, by following formula (I ') expression contain carboxyl (methyl) acrylate,
Formula (I ') in, R represents hydrogen atom or methyl, A represents alkylidene group.
3. manufacture method that contains carboxyl (methyl) acrylate, it is the described manufacture method that contains carboxyl (methyl) acrylate of claim 1, it is characterized in that, make the 5-norbornylene of representing by following formula II-2,3-dicarboxylic anhydride and hydroxyalkyl (methyl) acrylate of being represented by following formula III react
In the formula III, R represents hydrogen atom or methyl, and A represents alkylidene group.
4. manufacture method that contains carboxyl (methyl) acrylate, it is the described manufacture method that contains carboxyl (methyl) acrylate of claim 2, it is characterized in that, make norbornane-2 by following formula (II ') expression, 3-dicarboxylic anhydride and hydroxyalkyl (methyl) acrylate of being represented by following formula III react
In the formula III, R represents hydrogen atom or methyl, and A represents alkylidene group.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009121986A JP2010270041A (en) | 2009-05-20 | 2009-05-20 | Carboxy group-containing (meth)acrylic ester and method for producing the same |
| JP2009-121986 | 2009-05-20 | ||
| JP2009-208113 | 2009-09-09 | ||
| JP2009208113A JP2011057604A (en) | 2009-09-09 | 2009-09-09 | Carboxy group-containing (meth)acrylic acid ester and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101891619A true CN101891619A (en) | 2010-11-24 |
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ID=43100998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101828497A Pending CN101891619A (en) | 2009-05-20 | 2010-05-19 | Contain carboxyl (methyl) acrylate and manufacture method thereof |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20100125187A (en) |
| CN (1) | CN101891619A (en) |
| TW (1) | TW201105629A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501463A (en) * | 2017-07-17 | 2017-12-22 | 中山大学 | A kind of ultraviolet light self-crosslinking polyacrylates and preparation method thereof |
| CN112543791A (en) * | 2018-05-31 | 2021-03-23 | 根特大学 | Polymers based on bifunctional modified biopolymers and hydrogels which can be obtained from such polymers based on bifunctional modified biopolymers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1013095A (en) * | 1971-08-05 | 1977-06-28 | Carlos M. Samour | Pressure-sensitive adhesive polymers derived from acryloyloxyalkyl and methacryloyloxyalkyl acid esters |
| JP2005208366A (en) * | 2004-01-23 | 2005-08-04 | Fuji Photo Film Co Ltd | Positive resist composition and pattern forming method using the same |
| US20050282082A1 (en) * | 2004-06-21 | 2005-12-22 | Shin-Etsu Chemical Co., Ltd. | Polymer, resist composition and patterning process |
| KR20080010808A (en) * | 2006-07-28 | 2008-01-31 | 주식회사 코오롱 | Photoresist resin composition for column spacer |
-
2010
- 2010-05-18 KR KR1020100046493A patent/KR20100125187A/en not_active Application Discontinuation
- 2010-05-19 TW TW99115947A patent/TW201105629A/en unknown
- 2010-05-19 CN CN2010101828497A patent/CN101891619A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1013095A (en) * | 1971-08-05 | 1977-06-28 | Carlos M. Samour | Pressure-sensitive adhesive polymers derived from acryloyloxyalkyl and methacryloyloxyalkyl acid esters |
| JP2005208366A (en) * | 2004-01-23 | 2005-08-04 | Fuji Photo Film Co Ltd | Positive resist composition and pattern forming method using the same |
| US20050282082A1 (en) * | 2004-06-21 | 2005-12-22 | Shin-Etsu Chemical Co., Ltd. | Polymer, resist composition and patterning process |
| KR20080010808A (en) * | 2006-07-28 | 2008-01-31 | 주식회사 코오롱 | Photoresist resin composition for column spacer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501463A (en) * | 2017-07-17 | 2017-12-22 | 中山大学 | A kind of ultraviolet light self-crosslinking polyacrylates and preparation method thereof |
| CN107501463B (en) * | 2017-07-17 | 2020-03-20 | 中山大学 | Ultraviolet self-crosslinking polyacrylate and preparation method thereof |
| CN112543791A (en) * | 2018-05-31 | 2021-03-23 | 根特大学 | Polymers based on bifunctional modified biopolymers and hydrogels which can be obtained from such polymers based on bifunctional modified biopolymers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20100125187A (en) | 2010-11-30 |
| TW201105629A (en) | 2011-02-16 |
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Application publication date: 20101124 |